Solvents containing nitriles



Patented Jan. 22, 1952 Howard Hartough, litmam and fHowardW.SheldonyWoodh'ury, N J., axssignorslt'o Soconyf- Vacuum? Oil Companration of New York i y, Incorporated,` agcorpo- ApplicationQctoberis,,1947;Seria1No. 180,208`

The presentiinvention relates tousolvents` for natural and syntheticresins, gums, etccand, more particularly,v to composite solvents e of:more than linear -kauri-butanol number.` i

As pointed out by. W. J. Sweeney andJ. A; Tilton in Industrial v.andEngineering Chemistry for June 1934, Them widespread use of#` syntheticresins-for example thesphenolformaldehyde and thealkyd, or Glyptaltypeshas created demands4 for naphthas of `1 higher. solvency-than; thecommon run of `petroleum solventsmarketed in the past. While .'the.`coal-"tar solventssuch-as toluene and high-flash naphtha possess fhighsolvencyk powers,` they i have i' certain objectionable properties,Y inparticular :poor odor.

The gum kauri-butanol test is frequently utilized by both.;theoiLQrener" and the trade for evaluating solvent naphthas.` Thistestconsists essentially of titrating grams f `of a standard gum kaurisolution (100 grams of'gumkauridissolved in llgrauis-onfbutanol)` ina200 centimeter Ehrlenmeyer flask with the solvent to be tested;l The endpoint is reached Whenthe normally clear liquid acquires a slightturbidity.

This is determinedby placing aprinted page (10- i point print) "beneaththe -ilaskI and notingwhen the print, asviewed;` through the solution,just becomes blurred. 'I'he number of cubic centimeters of`solvent-required to produce` this end point is called thekami-butanolvalue\of the solvent. i i

It has nowbeen discovered' thatthewkauributanol values of solvents canbe enhanced in more than a linear proportion by combining recognizedsolvents with aromatic nitriles. This is surprising since it is to beexpected that a mixture of two solvents would have a kauri-butanol valueclosely approximating the weighted average of the kauri-butanol valuesof the solvent and the aromatic nitrile. For example, the kauributanolvalue for benzene is 103 and that for benzonitrile is 122. It would beexpected that a blend containing 50 volume per cent of each Would have akauri-butanol value of 115. However, a blend containing 50 volume percent of benzene and 50 volume per cent of benzonitrile has akauri-butanol value of 139. Accordingly, it is an object of the presentinvention to provide a multicomponent solvent having a kauributanolvalue greater than the calculated weighted average kauri-butanol valuefor the components. It is another object of the present invention toprovide multicomponent solvents containing an amount of an organicnitrile effective to produce a kami-butanol value for themulticomiclaim. (C1. 10s-311) 2 ponent solventgreater thanthe calculatedweightedhaverage of fthefkauri-butanolvaluesz: off the components. Willbecome apparenttoL those skilled infthe artfrom the followingvdescription takenin conjuncf tionrwith the drawings in which, i

Figure 1Y is a graph of the `observed:andra/leu-` lated rlrauri-butanolvalues; forV various mixtures` benzeneand benzonitrile; Y Figure 2 is a`graph of lthe'observed and `(salou--` lated' kauri-butanol values for fvarious :mixtures of r1-hexane andfbenzonitrile; Y

Figure 3 is a graph off'the observed andcalculated kauri-butanolivalues, for various: mixtures cfibenzonitrile` and an aromatic petroleumstock having a boiling range of 275 degreestof375fde,.` greesAFahrenheit and comprisingL a .mixture ofA polyalkyl benzenes paraflins.`andlnaphthenes,

the polyalkyl benzenes being predominantly di` methyl benzenes; andff iy Figure Al isa graph of `observed and calculated kauri-butanol valuesfor various mixturesof benzonitrile and anintermediate petroleumnaphthal aromatic hydrocarbons mixedwith benzonitrile have Va slopeioramountsof benzonitrile up tov50 volume per cent diierent than theslopes of curves for mixtures of aliphatic or predominantly aliphaticsolvents and up to 50 volume per cent of benzonitrile. Thus, forexample, the kami-butanol value for a volume per cent benzene-10 volumeper cent benzonitrile mixture is while the calculated value is 105. Thisrepresents an increase of 19 per cent of the calculated kauributanolvalue. Similarly, the observed kauributanol value for a 90 volume percent aromatic petroleum stock-10 volume per cent benzonitrile mixture is98 while the calculated value is 83 or an increase of 18 per cent. Onthe other hand, the observed kauri-butanol value for a 90 volume percent intermediate naphtha-l volume per cent benzonitrile mixture is 48While the calculated value is 45; an increase of about 7 per cent.Similarly, the calculated kauri-butanol value for a 90 volume per centn-hexane-lO volume per cent benzonitrile mixture is 36 and the observedvalue is 36. The following table provides a com- 55 parison of theeffect of adding varying amounts Other objects and advantages l ofbenonitrile, an aromatic nitrile to various solvents.

butanol value of the mixture being the sum of the kauri-butanol valuesof each component Benzene, Aromatic petroleum stock, Intermediatenaptha, n-hexane, kauri-butanol value kami-butanol value kami-butanolvalue kauri-butanol value Vol. Per Vol. Per Centgrnzo- SClent t m e o,ven Y Per cent Per cent v Percent 1 Per cent f obs. cal` inc. obs. cal.ma obs. cal. Vinc. obs. cal. ine

100 103 79 36 28 2 98 115 103 11. 7 83 80 3. 7 39 39 29,. 29 5 95 120104 15. 4 88 481. 8. 6 40 40 31 31 90 125 105 19. 0VV 99 83 19. 3 i 4845 6.7 36 36 80 132 107 22. 2 115 88 30. 7 06 54 22. 2 50 45 11. 1 70135 109 V18. 2 128 92 39. 2 88 62 25. 8 75 55 36. 4 60 138 111 23. 2 13796 42. 7 108 70 54. 3 100 65 53. 9 50 139 113 20.8 142 100 42. 0 127 8058.8 118 74 59. 5 40 138 114 21. 0, 144 108 33. 3 139 88 57. 3 133 8360. 3 30 137 116 18. 1 141 109 29. 4 145 96 51. 0 140 93 50. 5 20 133118 12. 7 136 113 20. 4 145 105 38. 1 141 102 38. 3 10 130 120 8. 3 129117 10. 3 140 114 22. 8 136 112 21. 4 0 122 122 122 122 122 122 122 122The data presented in the table together with 20 multiphed by the volumeper cent of said comthe graphs of Figures 1 to 4 establish that fornon-aromatic or predominantly non-aromaticV solvents the minimum amountof added aromatic nitrile to produce a practical increase in thekauri-butanoi value is about 20 volume per cent. However, for aromaticor predominantly aromatic solvents the minimum amount of added aromaticnitrile to produce a practical increase in the kauri-butanol value isabout 2 to about 10 volume per cent. Accordingly, the minimum effectiveconcentration of aromatic ntrile in the multicomponent solvent is about2 volume per centV when the basic solvent is predominantly aromatic innature and about 20volume per cent when the basic solvent ispredominantly nonaromatic in nature. It is also to be noted thatconcentrationsof aromatic nitrile in excess of about '70 volume per centof the total multicomponent solvent are ineffective to produce enhancedkauri-butanol values when the basic solvent is predominantly aromatic incharacter whereas concentrations as high as 80 volume per cent of themulticomponent solvent are eiective to produce enhanced kauri-butanolvalues when thebasic solvent is predominantly non-aromatic in character.Thus, the novel multicomponent solvent comprises an aromatic nitrile andone or more hydrocarbons, the mixture containing a concentration ofaromatic nitrile effective to produce kauri-butanol values at least 10per cent greater than the calculated kauri-butanol value Y of themixture, the calculated kaurponent in vthe multicomponent solvent.

We claim: i

A multicomponent solvent for resins, gums, and the like which consistsessentially of a predominantly aromatic hydrocarbon solvent for resins,

gums, and the like and benzonitrile, said benzo- REFERENCES CITED Thefollowing references are of record in the le of this patent:

UNITED STATES PATENTS Y Date Number Name 2,388,082 Roediger Oct. 30,1945 2,450,639 Denton etal. Oct. 5, 1948 2,508,215

Bishop May 16, 1950 OTHER REFERENCES Journal of Chemical Society,Article by Martin and Collie, pp. 26587-65 (1932).

Journal American Chemical Society, vol 24, 1902, Bozert and Hand, pp.1031-1032.

